Industrial Crops and Products 50 (2013) 550556

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Industrial Crops and Products

journal homepage: www.elsevier.com/locate/indcrop

Development of eco-friendly polyurethane coatings based on neem oil polyetheramide

Ashok Chaudhari a , Vikas Gite a, , Sandip Rajput a , Pramod Mahulikar a , Ravindra Kulkarni b
a b

Department of Polymer Chemistry, School of Chemical Sciences, North Maharashtra University, Jalgaon 425001, Maharashtra, India School of Chemical Technology, North Maharashtra University, Jalgaon 425001, Maharashtra, India

a r t i c l e

i n f o

a b s t r a c t
Renewable sources like vegetable oils have been used to prepare many polymeric resins and the topic is gaining more importance due to the functional attributes to structure of oils. In the regard, renewable source based polyurethane coatings have been prepared from polyetheramide of neem oil in the laboratory. In the preparation of polyetheramide, rst neem oil was allowed to react with diethanol amine. Obtained fatty amide was modied to the polyetheramide by reacting it with bisphenol-A. Spectroscopic techniques such as FT-IR and 1 H NMR conrmed the structures of fatty amide and polyetheramide. Polyurethane coatings were prepared from the polyetheramide by treating it with methylene diphenyl diisocyanate. Coating properties such as gloss, scratch hardness, adhesion, exibility, thermal stability, impact and chemical resistances were evaluated using standard methods. The inuence of surface modied TiO2 nano particles on the properties of the neem oil based polyurethane coatings was examined by loading nano TiO2 from 0 to 4%. The overall performance of coatings revealed that neem oil based polymeric coatings can be successfully used as coatings in industrial applications. Crown Copyright 2013 Published by Elsevier B.V. All rights reserved.

Article history: Received 24 May 2013 Received in revised form 23 July 2013 Accepted 4 August 2013 Keywords: Neem oil polyetheramide Eco-friendly polyurethane coatings TiO2 nano particles Renewable sources

1. Introduction The demand for polymers prepared from renewable sources is on the increase because of a number of reasons notably environmental concern, abundant availability and low price of renewable sources (Anand et al., 2012; Guner et al., 2006; Lligadas et al., 2012). Cellulose and vegetable oils are two major renewable sources present on the earth in large quantities. Applications of cellulose in polymeric coatings is limited while vegetable oils have been used most of the time to prepare polymeric binders for coatings formulations, ooring materials and resin applications (Gu et al., 2012; Opera, 2010). Vegetable oils obtained from different sources have also been widely used in preparation of inks, diluents, plasticizers, lubricants, agrochemicals, food industries, composite materials, etc. (Derksen et al., 1996; Kashif et al., 2011; Khot et al., 2001; Sharmin et al., 2006). Vegetable oils can be commonly converted

Abbreviations: IPDI, Isophorone diisocyanate; MDI, Methylene diphenyl diisocyanate; PEthA, Polyetheramide; PEA, Polyesteramide; TTIP, Titanium isopropoxide; THF, Tetrahydrofuran; TEVS, Vinyltriethoxysilane; DBTDL, Dibutyltin dilaurate; MS, Mild steel; AIJFA, Azadirachta indica juss fattyamide; PU, Polyurethane. Corresponding author. Tel.: +91 257 2257431; fax: +91 257 2258403. E-mail addresses: vikasgite123@gmail.com, vikasgite2000@yahoo.com (V. Gite).

into derivatives such as alkyd resins and polyols based on alkyds (Nimbalkar and Athawale, 2010). Polyols are low molecular weight polymers that may be reacted with different diisocyanates such as isophorone diisocyanate (IPDI), methylene diphenyl diisocyanate (MDI) or others, to obtain polyurethane (PU) coatings (Gite et al., 2010). A number of reports have described the preparation of polyols from different vegetable oils such as jatropha, soya, cottonseed, linseed, neem oils and their subsequent use in the preparation of PU (Chaudhari et al., 2013a,b; Gite et al., 2006; Jaliliana et al., 2010; Meshram et al., 2013a,b; Zlantanic et al., 2004). PU of the kind of interpenetrating polymer networks have also been prepared using castor oil with styrenic-acrylic polymers and these have gained much attention due to their interesting properties (Meier et al., 2007). Epoxidized soybean oil has been studied by curing with various cyclic acid anhydrides in presence of tertiary amines (Gerbase et al., 2002). Recent routes explored utilization of vegetable oils in coatings by preparing polyetheramides (PEthA) (Akintayo and Akintayo, 2010; Alam et al., 2004) and polyesteramides (PEA) (Dutta and Karak, 2005; Shende et al., 2004; Zafar et al., 2004). Azadirachta indica juss can be said to be underutilized when its available production potential is compared to its present limited applications in pharmaceuticals (Biswas et al., 2002) and agrochemicals sector as medicinal compound and bio pesticide (Bagle et al., 2013) respectively. Neem seed oil contains three

0926-6690/$ see front matter. Crown Copyright 2013 Published by Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.indcrop.2013.08.018

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O CH2 O C R CH O C R O CH2 O C R O Neem oil

CH2 CH2 OH

HN CH2 CH2 OH

NaOCH3 120 0C

HO CH2 CH2 N O C R

CH2 CH2 OH

CH2 OH

CH OH CH2 OH

Diethanol amine

Diethanol amide (AIJFA)

Fig. 1. Synthesis of AIJFA.

Glycerol

saturated fatty acids including palmitic (11.90%), stearic (29.96%) and arachidic (2.94%) acids. It also contains two unsaturated fatty acids viz. oleic (50.04%) and linoleic (5.15%) acids (Chaudhari et al., 2013a). Although neem plant is widely cultivated in arid zones of India with annual neem oil production rate of 18,000 ton, the utilization of the seed oil in the development of polymeric resins has not been investigated except our earlier report (Chaudhari et al., 2013a). Our previous report claims preparation of PU coatings from neem oil fatty amide using diisocyanate. In the present work, further chemical modication of fatty amide (AIJFA) prepared from neem oil has been carried to obtain polyetheramide (PEthA). The synthesized PEthA was treated with diisocyanate at room temperature to prepare the PU coatings. Effects of percent loading of silane modied nano TiO2 on the performance of pristine neem oil PEthA based PU coatings have been investigated rst time. Performance of PU coatings was evaluated using standard methods.

2.4. Synthesis of nano TiO2 and their modication by silane coupling agent Nano TiO2 was synthesized (Mahshid et al., 2006) and modied by using vinyltriethoxysilane (TEVS) coupling agent as reported in the literature (Chaudhari et al., 2013b; Sabzi et al., 2009). 2.5. Preparation of PU coatings based on PEthA PU coatings were obtained (Fig. 3) by reacting PEthA at room temperature with MDI using NCO/OH ratio 1.1:1 in the presence of a catalyst DBTDL (0.5%). In a typical process 50% solid content solution of PEthA was prepared in cyclohexanone and THF (80:20) mixture. PU were coded as PU0, PU1, PU2, PU3 and PU4 where sufx 04 indicated the percentage of modied nano TiO2 ranging from 0 to 4% (based on amount of PEthA) in PU coatings. After addition of nano TiO2 , reaction mixtures were sonicated on a sonicator for the proper dispersion of modied nano TiO2 and then mixture was treated with MDI. The entire reaction mixture was stirred for next 5 min at room temperature to attain pourable viscosity. This mixture was applied as a coating by using bar applicator on MS steel panels of 4 6 in. dimensions. The prepared coating panels were allowed curing at room temperature under visual examination. Prior to application of the coatings, the steel panels were pretreated by sand paper and washed with acetone. 3. Characterization 3.1. Chemical analysis Neem oil, AIJFA and PEthA were characterized for specic gravity (ASTM D5355 - 95), refractive index (ASTM D1747 - 09), saponication (ASTM D464 - 05), acid (ASTM D5768 - 02), hydroxyl (ASTM D1957-86) and iodine values (ASTM D5768-02). 3.2. Spectroscopic analysis The FT-IR spectra of the prepared resins were recorded on FTIR spectrophotometer (Shimadzu, Japan, Model No. 8400) from the range of 4000500 cm1 as KBr pellets. Homogenous mixture of sample in KBr was prepared by grinding in mortar and by the action of 12 ton lab press to diminish moisture present in the sample. 1 HNMR spectra of samples were recorded on Varian Mercury 300 MHz spectrometer using TMS as an internal standard in presence of CDCl3 as a solvent. 3.3. Transmission electron microscopy (TEM) The synthesized nano titanium dioxide particles were studied for their size by using TEM (TEM, Philips, CM-200, Holland). The analysis was carried out by accelerating voltage in the range of

2. Experimental 2.1. Chemicals and materials Neem seed oil was purchased from local supplier and used as it is. MDI, bisphenol-A, titanium isopropoxide (TTIP), vinyltriethoxysilane (TEVS) and dibutyltin dilaurate (DBTDL) (Aldrich Chemicals, UK) were of laboratory grade. Cylcohexanone, tetrahydrofuran and diethanolamine of analytical grade were obtained from s.d. ne-chemicals Ltd., India.

2.2. Synthesis of A. indica juss fatty amide (AIJFA) AIJFA was synthesized (Fig. 1) according to our earlier report (Chaudhari et al., 2013a).

2.3. Synthesis of polyetheramide (PEthA) Mixture of AIJFA (20 g, 0.10 M) and bisphenol-A (16.65 g, 0.073 M) were reacted (Fig. 2) in round bottom ask equipped with Dean and Stark trap, nitrogen inlet tube, thermometer and rota mental. The mixture was allowed to react by dissolving it in a mixture of solvents (80:20 parts of xylene and n-butanone) in presence of dilute sulfuric acid as a catalyst. The reaction mixture was heated at 175 5 C and reuxed until the theoretical amount of water was collected in Dean and Stark trap. Once the theoretical amount of water removed, reaction was allowed to stop. After the completion of reaction, solvent was evaporated in a rotary vacuum evaporator under reduced pressure to obtain PEthA.

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HO CH2 CH 2

CH2 CH2 OH + N

CH3 HO C CH3 OH

O C R
Dil. H2SO4

Diethanol amide (AIJFA)

R = Fatty acid chain

Bisphenol - A

CH3 H O CH 2 CH2 N O C R Polyetheramide (PEthA)

Fig. 2. Synthesis of polyetheramide (PEthA).

CH 2 CH2 O

C CH3

n CH2 CH2 CH2 CH2 OH N O C R

by dispersing TiO2 in acetone 20200 kV with resolution of 2.4 A with ultrasonic wave for sufcient time. Samples were deposited on Cu grid and viewed at high magnication. 3.4. Field emission scanning electron microscopy (FE-SEM) Morphologies of TiO2 nano particles and silane modied TiO2 nano particles were studied using thin layer of samples coated with gold on a FESEM (FE-SEM, HITAHCI High Technologies Corporation, Japan, Model No. S-4800) with voltage range from 0.5 to 30 kV. 3.5. PU coatings characterizations The PU coating panels were tested for the gloss (Model BYK Additive & Instruments, Germany) measurement at an angle of 60 on the calibrated digital gloss meter. Elasticity of the prepared coatings was measured in the range of 45180 angles by using the conical mandrel instrument (Raj Scientic Company, Mumbai). Pencil hardness of the coatings was measured with the pencil hardness tester (Model BYK Additive & Instruments, Germany) according to ASTM D-3363 standards. Adhesion of coatings (ASTM D-3359-02) was tested on the cross cut adhesion tester (model

no 107, Elcometer, U.K.) consisting of a die with 11 number of closed set of parallel blades. For measurement of impact resistance, PU coated panels were deformed rapidly by application of the weighted indenter (1.818 lb) from variable heights starting from 5 to 40 in. of the tubular impact tester. After falling weighted indenter peeling and cracking of the coatings from substrate was examined. 3.6. Chemical resistance For estimating chemical resistance (ASTM D 543-67/1972) of coatings, sample panels were dipped in 5% alkali solutions (NaOH and NH4 OH), 25% acid solutions (H2 SO4 and CH3 COOH) and a solvent (xylene) for 7 days. During the test, the panels were taken out every day for once from solutions. Softness, loss in gloss, loss in adhesion, blister and rupture were examined during the test. 3.7. Thermal analysis of PU coatings Thermal behavior of the prepared PU coatings was studied by the thermo gravimetric analysis (Model - TGA 4000, PerkinElmer, USA) in the range of 30600 C temperature at heating rate of 20 C/min in presence of N2 as an inert atmosphere.

CH3 H O CH2 CH2 CH2 CH2 O N OC R PEthA DBTDL CH3 CH2 CH2 N O C R CH2 CH2 O C CH3 O O CH2 CH2 CH2 CH2 n O C NH N O C R PU coatings
Fig. 3. Preparation of PU coatings.

C CH3

O n CH2 CH2 CH2 CH2 OH + OCN N O C R

CH2

NCO

MDI

O CH2 NH C O

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75 70 65 60 %T
1886.44

55
2333.94

50 45 40

1363.72

642.32 563.23

939.36

nitrogen as it is less electronegative, while peaks at 2.212.40 ppm were assigned to CH2 linked to amide carbonyl. Peaks seen at 2.012.15 ppm were of CH2 attached to olenic double bonds and peak at 1.35 ppm was of internal CH2 of fatty amide chain. Methylene protons attached to the hydroxyl OH were seen at 3.403.45 ppm. Proton of OH occurred at 5.91 ppm. Characteristic peak of olenic unsaturation occurred at 5.11 ppm. From 1 H NMR data we conrmed the structure of PEthA as proposed in the Fig. 5. 4.5. TEM images of nano TiO2 The particle size of the TiO2 nano particles was found to be in the range of 100150 nm, as conrmed by transmission electron microscopy and it is shown in Fig. 6. 4.6. SEM images of nano TiO2

1610.61

1064.74

30 25 20 3600 Liquid

2929.97 2858.60

3300.31

2800

2000

1600

1200

1246.06

800 600 400 1/cm

Fig. 4. FTIR spectral analysis of neem oil based PEthA.

831.35

35

1460.16

4. Results and discussion 4.1. Characteristic properties of neem oil, AIJFA and PEthA Specic gravity, refractive index, saponication, acid, hydroxyl and iodine values of raw materials are given in the Table 1. Specic gravity increased in the sequence of neem oil, AIJFA and PEthA, while iodine value was decreased for the same sequence. The hydroxyl value also decreased from AIJFA to PEthA. The trend may be due to increase in molar masses from neem oil to AIJFA and PEthA. 4.2. Spectroscopic analysis of AIJFA The formation of AIJFA was conrmed by FT-IR and 1 H NMR spectral analysis according to our earlier report (Chaudhari et al., 2013a). 4.3. FTIR of PEthA Fig. 4 is a FTIR spectrum presenting the frequencies of functional groups of PEthA prepared from neem oil. The spectrum showed a broad band at 3300 cm1 indicating presence of OH stretching of PEthA. The characteristic bands at 1246 cm1 and 1064 cm1 were due to aryl alkyl ether linkages for C O C asymmetrical and symmetrical stretchings. Absorption bands at 2859 and 2930 cm 1 were attributed to symmetrical and asymmetrical stretchings of CH2 and CH3 groups respectively. The characteristic band at 1611 cm1 indicated the presence of C O stretching of amide carbonyl group and 1460 cm1 indicated the C N stretching vibrations. The characteristic absorption bands at 831939 cm1 represented the presence of aromatic ring of bisphenol-A in PEthA. 4.4.
1H

The morphology of nano and silane modied nano TiO2 were investigated by FE-SEM images. SEM image of unmodied TiO2 particles showed aggregates and sharp edges (Fig. 7a), while silane modied nano TiO2 (Fig. 7b) particles were spherical in shape and without sharp edges. The modication of TiO2 may have resulted into the minimum agglomeration of nano particles. These modied individual particles may have good tendency to disperse in an organic media like PU coatings because of hydrophobic nature of modied nano TiO2 particles. SEM images of the modied nano TiO2 showed upto 200 nm. 4.7. Coating properties The polyetheramide based polyurethane coatings containing nano TiO2 were applied on the MS panels using the bar coater and the evaluated coating properties are given in Table 2. Surface dry time of PU-0, PU-1 PU-2, PU-3 and PU-4 coatings were found to be 27, 21, 20, 19 and 20 min respectively. This indicated that increase in the % of TiO2 decreased the curing time of coatings upto 3% nano TiO2 . Scratch hardness and cross cut adhesion of coatings were increased in PU-0, PU-1 and PU-2 while it decreased in the case of PU-3 and PU-4. This may be due to poor dispersion of the nano TiO2 at higher loadings. In the case of gloss, it was observed that as amount of modied nano TiO2 in PU coatings increased, gloss was also increased from 92 to 98. Impact resistance and pensile hardness of the coatings were found to increase upto 3% nano TiO2 and then decreased. All PU samples passed the mandrell exibility test and no kind of failure was observed. It was found that the prepared PU samples displayed good resistance to acids, alkalis and solvent. Chemical resistance test showed no signicant changes in the appearance of coatings, after exposing them to acids, alkalis and solvent. In acid specimens, slight loss in gloss was found after drying the panels. In general we can say the PU prepared from neem oil polyetheramide showed good resistance toward acids, alkalis and solvent. 4.8. Thermo gravimetric analysis (TGA) Thermograms of the PU samples prepared from PEthA and effect of percent of nano TiO2 on PU are given in Fig. 8. TGA curves of all the coating samples showed three steps degradation. First step degradation was started in the range of 220247 C and degradation resulted into 0714% weight losses for all PEthA based PU coatings which was attributed to the decomposition of urethane moieties. Second step degradation started in between 313 and 316 C temperature and degradation resulted in 2835% weight losses. This second stage degradation may be due to the decomposition of parts contributed by polyol (soft segment). Last or third step degradation took place in the range of 433451 C and resulted in 5275% weight

NMR spectra of PEthA

NMR spectra of PEthA is shown in Fig. 5. The 1 H NMR spectra revealed peaks for protons of aromatic ring (bisphenol-A moiety) around 7.126.62 ppm, which was shifted to the downeld because aromatic ring is attached to electron donating oxygen atom. A proton of geminal dimethyl group was found around 1.23 ppm. The formation of ether linkages ( CH2 group attached to electron donating oxygen) through the reaction of AIJFA with bisphenol-A were conrmed by the appearance of peaks at downeld i.e. 4.014.28 ppm. Peaks in the range of 0.900.81 ppm were assigned to terminal CH3 of long fatty chain. Downeld peaks at 3.313.40 ppm were assigned to the CH2 attached to amide

1H

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Table 1 Characteristic properties of neem oil, AIJFA and PEthA. Properties Neem oil AIJFA PEthA Specic gravity 0.920 0.927 0.929 Refractive index 1.503 1.542 1.495 Sap value 186 Acid value 1.3 00 00 OH value 000 205 190 Iodine value 64.55 59.82 54.46

Fig. 5.

H NMR spectra of PEthA of neem oil.

Fig. 6. TEM images of nano TiO2 particles.

Table 2 PU coatings properties. Sample/properties PU-0 PU-1 PU-2 PU-3 PU-4 Dry to touch (min) 27 21 20 19 20 Scratch hardness (kg) 1.5 1.6 1.8 1.7 1.7 Cross cut adhesion (%) 96 97 98 97 96 Gloss 60 92 93 95 96 98 Impact resistance (lb in.) 58.18 61.81 65.45 67.27 63.63 Pencil hardness 2H 2H 3H 4H 3H

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555

Fig. 7. SEM images of unmodied and modied nano TiO2 .

100 80
PU0 PU1 PU2 PU3 PU4

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% wt loss

60 40 20 0 100 200 300 400

O

500

600

Temp ( C)
Fig. 8. TGA curve of PEthA based polyurethanes.

losses. Third step degradation may be a result of decomposition of hydrocarbon chains. Highest thermal stability was observed for the PU-2 sample at the second and last step, while least thermal stability was observed to the pristine PU-0 amongst all PEthA based PU coatings. All modied nano TiO2 loaded PU coatings showed better thermal stability than the pristine PU-0 sample. In the series thermal stability increased in the trend PU-0, PU-1, PU-3, PU-4 and PU-2. Initially thermal stability of the PU coatings increased with increase in amount of nano ller from 0 to 1 weight percent loading and then it increased for 3 and 4 weight percents. From the TGA of PU coatings, we can conclude that the PU-2 sample had superior thermal stability compared to all other samples.

5. Conclusions Neem oil based polyetheramide for PU coatings were prepared successfully. The neem oil fatty amide based polyetheramide and its intermediate were characterized by the proper techniques. The nano TiO2 were synthesized and modied by using the silane coupling agent. The presence of nano TiO2 signicantly increased gloss, pencil hardness, chemical resistance and thermal stability of the coatings. The neem oil based resins have good potential to be used as eco-friendly resins in surface coatings or can substitute to petroleum based binders.

Acknowledgement The authors would like to acknowledge to University Grants Commission (UGC), Govt. of India, New Delhi for nancial support to the present work.

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